CN102050690B - Isoolefine production method - Google Patents
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- CN102050690B CN102050690B CN200910236763.5A CN200910236763A CN102050690B CN 102050690 B CN102050690 B CN 102050690B CN 200910236763 A CN200910236763 A CN 200910236763A CN 102050690 B CN102050690 B CN 102050690B
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Abstract
The invention discloses an isoolefine production method comprising the following procedures: the tower top product of a second fraction column is obtained in gas phase; and the gas is heated to an ether cracking reaction temperature and enters into an ether cracking reaction vessel after compression. Therefore, gas phase condensation and repeated heating are avoided, required recirculated water and steam are less, the equipment energy consumption is lower, the operating pressure of the second fraction column is lower, the separation effect of the fraction column is improved, and the operation is facilitated. In the isoolefine production method, the gas phase reaction product at the outlet of the ether cracking reaction vessel is compressed to serve as the heat source for a fifth fraction column reboiler, and is sent to a third fraction column after condensation, so that the total steam amount and the recirculated water amount are reduced, and the equipment energy consumption is further lowered.
Description
Technical field
The present invention relates to a kind of production method of isoolefine, say further, relate to method or the direct method of preparing isoolefine by cracking tert-alkyl ether by least containing a kind of hydrocarbon mixture and reaction of at least one alcohol of isoolefine, preparing high purity tert-alkyl ether, by cracking tert-alkyl ether, prepare again isoolefine.
Background technology
Isoolefine, tert-alkyl ether are the important source material of fine chemistry industry, also be important intermediate raw material or the monomer of synthetic rubber, synthetic resins, as high-purity isobutylene, be widely used in producing the multiple Chemicals such as isoprene-isobutylene rubber, polyisobutene and methyl methacrylate; Methyl tertiary butyl ether (MTBE) is the raw material of preparing high-purity isoolefine, is again the important additives that improves fuel octane number.
Adopt tert-alkyl ether cracking and tert-alkyl ether to synthesize and combine preparing high-purity isoolefine with cracking, there is reaction preference high, do not have the advantages such as pollution and corrosion.Domestic industrialized tert-alkyl ether is synthetic as follows with cracking high purity tert-alkyl ether and high purity isoolefine general method at present:
The hydrocarbon mixture that contains isoolefine and alcohol are sent into the methyltertiarvbutyl ether reactor that catalyst for etherification is housed, obtain mainly containing the product of tert-alkyl ether, after two separation column separation, the high purity tert-alkyl ether cut obtaining, after the high purity tert-alkyl ether of gas phase is cooling, part is returned to this after-fractionating tower, to maintain the normal running of this tower; Part, with liquid form extraction, enters products pot, then this liquid-phase product is vaporized and be heated to scission reaction and send into cracking reactor after temperature required.Obtain mainly containing the product of unreacted tert-alkyl ether and isoolefine and alcohol, this cracking product obtains high purity isoolefine after taking off heavily, taking off light and extracting and separating.
Because high purity tert-alkyl ether product needs condensation from the separation of after-fractionating tank, and send into ether cracking reactor after heater via heating vaporization, the large usage quantity of water coolant and heating steam in this process, causes the energy consumption of Isoolefine production method process higher, and production cost is larger.
Summary of the invention
For solving in prior art, there is the problem that energy consumption is larger, the invention provides the synthetic production method of isoolefine processed of combining with cracking of a kind of improved tert-alkyl ether, adopt the method can reduce the water coolant of device and the consumption of heating steam, reduce the energy consumption of whole device.
The object of the invention is to provide a kind of Isoolefine production method, includes following operation:
(1) hydrocarbon mixture and at least one alcohol of at least containing a kind of isoolefine are sent into the methyltertiarvbutyl ether reactor R1 that catalyst for etherification is housed, to make the product P 1 that at least contains a kind of tert-alkyl ether;
(2) product P 1 operation (1) being obtained is sent into the first separation column C1, to obtain the organic fraction O1 that mainly contains unreacted hydrocarbon mixture, unreacting alcohol, a small amount of lower molecular weight ether light constituent and the fraction B 1 that mainly contains tert-alkyl ether, secondary alkyl oxide and low polyisoolefines heavy constituent;
(3) fraction B 1 that mainly contains tert-alkyl ether, secondary alkyl oxide and low polyisoolefines heavy constituent operation (2) being obtained is sent into after-fractionating tower C2, the fraction B 2 that obtains high purity tert-alkyl ether cut O2 and contain tert-alkyl ether, secondary alkyl oxide and low polyisoolefines heavy constituent;
(4) high purity tert-alkyl ether cut O2 heater via E1 heating operation (3) being obtained, after the first compressor K1 compression, with gas phase form, send into ether cracking reactor R2 again, obtain mainly containing the product P 2 of unreacted tert-alkyl ether and isoolefine and alcohol; After further separation, obtain isoolefine again,
The range of reaction temperature of methyltertiarvbutyl ether reactor R1 is 30 ℃～100 ℃, and preferable range is 40 ℃～90 ℃, and pressure range is 0.1～4.0MPa, and preferable range is 0.5～2.5MPa, and air speed scope is 0.01～50hr
-1, preferable range 0.1～10hr
-1, the alcohol that enters this methyltertiarvbutyl ether reactor can be the reuse alcohol from the 4th separation column C4, can be also fresh alcohol, the alcohol that enters described methyltertiarvbutyl ether reactor is 0.3～5.0 with the scope of the hydrocarbon mixture weight ratio that contains isoolefine, preferable range 0.5～3.0.
The working pressure scope of the first separation column C1 is at 0.1～2.0MPa, preferred 0.5～1.5MPa, and number of theoretical plate is between 3～80, preferably between 10～50.
The working pressure scope of after-fractionating tower C2 is at 0.02～2.0MPa, preferred 0.05～1.5MPa, and number of theoretical plate is between 3～80, preferably between 10～50.
The reaction pressure of ether cracking reactor R2 is that between 50 ℃～300 ℃, air speed is at 0.5～50h at range of reaction temperature between 0.3～1.5MPa
-1between.
Isoolefine production method of the present invention, can also comprise following operation:
(5) product P 2 operation (4) being obtained is with the extraction of gas phase form, after being condensed as the thermal source of follow-up the 5th separation column C5 reboiler, send into the 3rd separation column C3 after the second compressor compresses, to obtain the main fraction B 3 that contains the light constituent cut O3 of isoolefine, a small amount of alcohol, a small amount of lower molecular weight ether and mainly contain alcohol, unreacted tert-alkyl ether
The pressure range of the 3rd separation column C3 is at 0.2～1.2MPa, and preferably 0.3～0.8MPa number of theoretical plate is between 3～80, preferably between 10～50.
(6) the cut O3 the 3rd separation column C3 of operation (5) being obtained sends into water wash column T1, to obtain the aqueous phase B 4 of main moisture, alcohol and mainly to contain the organic phase O4 of isoolefine, a small amount of lower molecular weight ether light constituent,
Cut O3 is 0.005～20 with the water weight ratio that enters water wash column T1, preferably 0.01～5, and the pressure range of washing disengaging zone is 0.1～2.0MPa, preferred 0.1～1.5MPa, temperature range is 10 ℃～60 ℃.
(7) aqueous phase B 4 operation (6) being obtained is sent into the 4th separation column C4, to obtain aqueous distillate B5 and the rich alcohol cut O5 of poor alcohol, rich alcohol cut O5 described at least a portion is circulated to the methyltertiarvbutyl ether reactor R1 of operation (1), aqueous distillate B5 described at least a portion is circulated to water wash column T1
The pressure range of the 4th separation column C4 is 0.1～1.2MPa, and preferably 0.1～0.8MPa number of theoretical plate is between 3～80, preferably between 10～50.
(8) organic phase (O4) operation (6) being obtained is sent into the 5th separation column C5, to obtain main light constituent cut O6 and high purity isoolefine fraction B 6 containing lower molecular weight ether, light constituent cut O6 described at least a portion is circulated to methyltertiarvbutyl ether reactor R1.
The pressure range of the 5th separation column C5 is 0.1～1.5MPa, preferred 0.3～1.0MPa, and number of theoretical plate is between 3～80, preferably between 5～50.
In hydrocarbon material of the present invention at least containing a kind of isoolefine (tertiary olefin), also contain the components such as other saturated or unsaturated hydrocarbons, as the C from oil refining or petrochemical complex
3and/or C
4material, C
3and/or C
4steam cracking material (being generally the material of extraction after diene), from the material after isomerized catalytic pyrolysis material (hydrogenation isomerization and skeletal isomerization) and paraffin dehydrogenation, all can be used as hydrocarbon material of the present invention; Alcohol of the present invention is mainly the alcohol of 1-4 carbon atom, particular methanol and ethanol.Tert-alkyl ether prepared by available method of the present invention is mainly methyl tertiary butyl ether (MTBE), Ethyl Tertisry Butyl Ether (ETBE), ethyl pentyl group ether (ETAE), tertiary amyl-methyl ether (TAME), sec.-propyl tertbutyl ether etc., tertbutyl ether cracking obtains iso-butylene, the isoolefine that other tert-alkyl ether cracking obtains is a mixture, and as TAME, cracking obtains 2-methyl-2-butene and 2-methyl-1-butene alkene mixture.The pure isoolefine making with the synthetic and cracking integrated processes of tert-alkyl ether of the present invention on one of them double key carbon with the compound of branched-chain alkyl (methyl), these compounds are generally the isoolefine containing 4-8 carbon atom, preferably containing the isoolefine of 4-6 carbon atom, as iso-butylene and isopentene, dissident's alkene, isooctene, isodecyl alkene etc.
Methyltertiarvbutyl ether reactor of the prior art all can be used for the present invention, as catalyticreactor, catalytic distillation reactor etc.Catalyst for etherification can be any catalyzer that can be used for isoolefine etherificate of the prior art, as an acidic catalyst (being generally the solid acid catalyst being formed by organic acid acetic) and mineral acid ester catalyst, the present invention preferentially selects solid acid resin catalyst as Amberlyst 15 or 35.
Below in conjunction with accompanying drawing, Isoolefine production method of the present invention is described further.
Tert-alkyl ether of the present invention is synthetic comprises operation (1), operation (2), operation (3) and operation (4) with cracking for the production method (referring to accompanying drawing) of isoolefine, in operation (1), hydrocarbon mixture and at least one alcohol of at least containing a kind of isoolefine are sent into the methyltertiarvbutyl ether reactor R1 that catalyst for etherification is housed through pipeline 1,2 and 3 respectively, obtain at least containing a kind of product P 1 of tert-alkyl ether.In operation (2), to obtain at least a portion etherification product P1 by operation (1) and send into the first separation column C1 through pipeline 4, tower top obtains mainly containing the organic fraction O1 of unreacted hydrocarbon mixture, unreacting alcohol, a small amount of lower molecular weight ether light constituent, organic fraction O1 can be used as Organic Chemicals, or is used as liquefied fuel gas etc. after removing alcohol; The fraction B 1 that obtains mainly containing tert-alkyl ether, secondary alkyl oxide and low polyisoolefines heavy constituent at the bottom of tower, tower bottom distillate B1 can be used as fuel dope, and the after-fractionating tower C2 that also can send in operation 3 through pipeline 6 carries out further separation.In operation (3), the tower bottom distillate B1 that the first separation column C1 in operation (2) is obtained sends into after-fractionating tower C2 fractionation, at the bottom of after-fractionating tower C2 tower, obtain the fraction B 2 that contains tert-alkyl ether, secondary alkyl oxide and low polyisoolefines heavy constituent, tower bottom distillate B2 can be used as fuel dope; After-fractionating tower C2 overhead product gas phase extraction high purity tert-alkyl ether O2 sends into operation 4; In operation 4, the high purity tert-alkyl ether O2 that operation 3 obtains gas phase is when pipeline 7 is sent into well heater E1 (as steam heater etc.) and is heated to cracking temperature, through pipeline 7a, send into the first compressor K1 again, the pressure of compressor outlet material is greater than after cracking reactor working pressure, through pipeline 7b, enter the ether cracking reactor R2 that ether catalyst for cracking is housed, obtain the product P 2 that contains at least one at least one alcohol of isoolefine, then through further obtaining isoolefine after separation.
The production method of isoolefine of the present invention also comprises operation (5), (6), (7), (8).(referring to accompanying drawing), in operation (5), the product P that contains at least one at least one alcohol of isoolefine 2 that ether cracking reactor R2 in operation (4) is obtained, with gas phase form, through pipeline 9a, send into the second compressor K2 to improve pressure, through pipeline 9b, as the thermal source of the 5th separation column C5 reboiler E2, be cooled into liquid phase again and send into the 3rd separation column C3 by pipeline 9, obtain mainly containing the cut O3 of isoolefine, alcohol and lower molecular weight ether light constituent with containing the fraction B 3 of alcohol, unreacted tert-alkyl ether.At the bottom of the 3rd separation column C3 tower, at least a portion mainly can be back to methyltertiarvbutyl ether reactor R1 through pipeline 11,11a and 3 containing the fraction B 3 of alcohol and unreacted tert-alkyl ether, and another part cut can be discharged through pipeline 11 and 11b; The main cut O3 containing isoolefine, alcohol and lower molecular weight ether light constituent can be used as industrial chemicals or for further separated to obtain highly purified isoolefine product.
In operation (6), overhead fraction O3 from the 3rd separation column C3 is sent into water wash column T1 through pipeline 10,14, fresh water W1 is sent into water wash column T1 through pipeline 12, obtain the alcohol aqueous phase B 4 of main moisture, alcohol and mainly contain the organic phase O4 of isoolefine, a small amount of lower molecular weight ether light constituent, organic phase O4 can be used as Organic Chemicals or liquefied gas etc., also can carry out further separated to obtain highly purified isoolefine.
For the alcohol in alcohol aqueous phase B 4 at the bottom of further recovery water wash column T1 tower, in operation (7), the alcohol aqueous phase B 4 that contains from water wash column tower reactor is sent into the 4th separation column C4 through pipeline 13, to obtain aqueous distillate B5 and the rich alcohol cut O5 of poor alcohol.The rich alcohol cut O5 of at least a portion that tower top obtains (preferably most of) returns to methyltertiarvbutyl ether reactor R1 through pipeline 16,16a, 3, at least a portion at the bottom of the tower of the 4th separation column C4 (preferably most of) aqueous distillate B3 through managing 17,17a, 14 returns to water wash column T1, water at the bottom of the tower of the 4th a small amount of separation column C4 can be discharged through pipeline 17,17b.The water that enters water wash column T1 can be recirculated water at the bottom of the 4th separation column C4 tower adding through pipeline 17,17a, 14, the fresh water W1 that also can add by pipeline 12.
For further that light constituent in organic phase O4 is separated with isoolefine, to obtain high purity isoolefine, in operation (8), the organic phase O4 that obtains mainly containing isoolefine, a small amount of lower molecular weight ether light constituent from water wash column is sent into the 5th separation column C5 through pipeline 15, obtain mainly containing low molecule ether light constituent cut O6 and high purity isoolefine fraction B 6.High purity isoolefine B6 discharges through pipeline 19, can be used as polymer raw.Mainly containing low molecule ether light constituent cut O6 can discharge through pipeline 18,18b, also at least a portion overhead fraction O6 can be returned to methyltertiarvbutyl ether reactor R1 through pipeline 18,18a, the by products such as lower molecular weight ether that can suppress in methyltertiarvbutyl ether reactor R1 generate, and improve the selectivity of alcohol.
The present invention is condensed in a gas phase part for after-fractionating tower C2 extraction, to guarantee the backflow of this separation column, another part needs after temperature through being heated to, after the first compressor compresses, enter again ether-splitting solution reactor, not only can reduce the energy consumption of device, also reduce the working pressure of after-fractionating tower, improved the separating effect of separation column, be more conducive to the operation of after-fractionating tower with separated.In addition, the present invention can be using the gas-phase reaction product of ether-splitting solution reactor outlet thermal source as follow-up the 5th separation column after the second compressor compresses, after being condensed, send into the 3rd separation column, can reduce like this steam consumption and recirculated water consumption, further reduce the energy consumption of device.
Sharpest edges of the present invention are for existing isoolefine plant modification project, do not need just can realize with equipment such as changing after-fractionating tower, have reduced production cost in the time of energy-conservation, have improved economic benefit.
Accompanying drawing explanation
Fig. 1 Isoolefine production method schema of the present invention (comprising C1, C2)
Fig. 2 Isoolefine production method schema of the present invention (comprising C1, C2, C3, C4, C5)
The operation that dotted line representative in figure may exist, containing of the main code name in figure means:
R1-methyltertiarvbutyl ether reactor C1-the first separation column
C2-after-fractionating tower E1-well heater
Interchanger (can be made the 5th separation column
R2-ether cracking reactor E2-
Reboiler)
C3-the 3rd separation column T1-water wash column
C4-the 4th separation column C5-the 5th separation column
K1-first compressor K2-the second compressor
E3-after-fractionating tower condenser
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.
Embodiments of the invention take methyl tertiary butyl ether synthetic with cracking process preparing high-purity iso-butylene (IB) and high-purity methyl tertbutyl ether (MTBE) cracking high-purity isobutylene as example illustrates production method of the present invention.Wherein the catalyzer of ether-splitting solution reactor charge is solid acid catalyst, is the method preparation adopting described in GB1173128 patent, and concrete preparation method is as follows: with aluminum sulfate aqueous solution, flood γ-Al
2o
3, be dried thereafter and within 3 hours, be prepared from 450 ℃ of roastings, on catalyzer, the content of sulfate radical is 20% (weight percent).While not specializing, from the material of separation column extraction, be liquid phase.
Raw material mixed c 4 is that the product of ethylene cracker (removes the cracking c_4 raw material after diene, from chemical industry one factory of Yanshan Mountain branch office of China Petrochemical Industry, lower same), the mixed c 4 hydrocarbon that contains iso-butylene and methyl alcohol are respectively through pipeline 1, 2 and 3 enter methyltertiarvbutyl ether reactor R1, in mixed c 4 hydrocarbon, the content of iso-butylene is 20.1% (weight) left and right, the material quantity that enters methyltertiarvbutyl ether reactor is 100kg/h, Amberlyst 15 solid acid resin catalysts (ROHM & HAAS production) are housed in methyltertiarvbutyl ether reactor R1, 60 ℃ of the temperature of reaction of methyltertiarvbutyl ether reactor R1, reaction pressure is 1.2MPa, the air speed 6hr of methyltertiarvbutyl ether reactor
-1.Entering the methyl alcohol of this methyltertiarvbutyl ether reactor and the weight ratio of iso-butylene is 0.6.Etherification product P1 enters the first separation column C1 through pipeline 4, the working pressure of the first separation column C1 is 0.6MPa, the number of theoretical plate of this tower is 35, the main fraction B 1 containing methyl tertiary butyl ether is by sending into after-fractionating tower C2 through pipeline 6 at the bottom of tower, the working pressure of after-fractionating tower C2 is 0.1MPa, the number of theoretical plate of this tower is 30, the cut O2 of top gaseous phase extraction high-purity methyl tertbutyl ether, when being heated to 180 ℃, steam heater E1 sends into the first compressor K1, compressor delivery pressure is 0.9MPa, temperature out is 200 ℃, enter again ether-splitting reactor R2, the reaction pressure of this ether cracking reactor is 0.85MPa, temperature of reaction is 200 ℃, reaction velocity is 2h
-1, method flow, referring to Fig. 1, adopts the inventive method, and the steam consumption of the cooling water and steam consumption of after-fractionating tower C2 and the feed heater of ether cracking reactor is in Table 1.
Comparative example 1
The mixed c 4 hydrocarbon that contains iso-butylene and methyl alcohol (MeOH) are respectively through pipeline 1, 2 and 3 enter methyltertiarvbutyl ether reactor R1, in mixed c 4 hydrocarbon, the content of iso-butylene is 20.1% (weight), the material quantity that enters methyltertiarvbutyl ether reactor is 100kg/h, etherification product P1 enters the first separation column C1 through pipeline 4, the main fraction B 1 containing methyl tertiary butyl ether is by sending into after-fractionating tower C2 through pipeline 6 at the bottom of tower, overhead extraction liquid phase high-purity methyl tertbutyl ether from after-fractionating tower C2, through steam heater E1, be heated to after 200 ℃, send into ether-splitting reactor R2, operation of equipment condition is all with embodiment 1, adopt the method, the steam consumption of the cooling water and steam consumption of after-fractionating tower C2 and the feed heater of ether cracking reactor is in Table 1.
Table 1
As can be seen from Table 1, the steam consumption of embodiment 1 and cooling water amount are starkly lower than steam consumption and the cooling water amount in comparative example 1, it can be said that bright employing the inventive method, be that the tower top material of after-fractionating tower C2 is with the extraction of gas phase form, and heater via is heated to temperature required, send into again after compression ether cracking reactor R2, with traditional iso-butylene preparation method comparison, the cooling load of condenser and the heating load of well heater E1 that have reduced after-fractionating tower C2, the energy consumption of device obviously reduces.
The mixed c 4 hydrocarbon that contains iso-butylene and methyl alcohol enter methyltertiarvbutyl ether reactor R1 through pipeline 1,2 and 3 respectively, in mixed c 4 hydrocarbon, the content of iso-butylene is 20.1% (weight), the material quantity that enters methyltertiarvbutyl ether reactor is 100kg/h, Amberlyst 15 solid acid resin catalysts (ROHM & HAAS production) are housed in methyltertiarvbutyl ether reactor R1,60 ℃ of the temperature of reaction of methyltertiarvbutyl ether reactor R1, reaction pressure is 1.2MPa, the air speed 6hr of methyltertiarvbutyl ether reactor
-1.Entering the methyl alcohol of this methyltertiarvbutyl ether reactor and the weight ratio of iso-butylene is 0.6.Etherification product P1 enters the first separation column C1 through pipeline 4, the working pressure of the first separation column C1 is 0.9MPa, the number of theoretical plate of this tower is 35, the main fraction B 1 containing methyl tertiary butyl ether is by sending into after-fractionating tower C2 through pipeline 6 at the bottom of tower, the working pressure of after-fractionating tower C2 is 0.5MPa, the number of theoretical plate of this tower is 30, the cut O2 of top gaseous phase extraction high-purity methyl tertbutyl ether, heater via is heated to 180 ℃, after being increased to 0.7MPa by pressure, the first compressor enters again ether-splitting reactor R2, the ether catalyst for cracking being equipped with in reactor R2 is solid acid catalyst (by the method preparation described in GB1173128 patent), its sulfate radical content is 20%, the reaction pressure of this ether cracking reactor is 0.55MPa, temperature of reaction is 200 ℃, reaction velocity is 2h-1, the product P 2 obtaining from ether cracking reactor boosts to 1.0MPa through the second compressor and is condensed into liquid phase as the thermal source of the 5th separation column reboiler E2, enter the 3rd separation column C3, the working pressure of the 3rd separation column C3 is 0.6MPa, number of theoretical plate is 25, the overhead fraction O3 of the 3rd separation column C3 enters water wash column T1 through pipeline 10 and 14, the working pressure of water wash column T1 is 0.6Mpa, service temperature is 40 ℃, fresh water W1 enters water wash column through pipeline 12 by tower top, the weight ratio of fresh water W1 and organic fraction O3 is 0.4, from the isolated organic phase O4 of water wash column tower top, through pipeline 15, send into the 5th separation column C5, the working pressure of separation column C5 is 0.7MPa, number of theoretical plate is 35, at the bottom of the 5th separation column C5 tower, obtain purity and be 99.95% iso-butylene, this product can be used as the monomer of polymerization product, its method flow (is not used the dotted line 16 in figure referring to Fig. 2, 16a, 18,18a, 11,11a, pipeline 9 and the 4th separation column C4), table 2～table 4 has provided mass flow and the composition that passes in and out each equipment in present method flow process.
Table 2
| R1 entrance cut (kg/h) | R1 exports cut P1 (kg/h) | C1 overhead fraction O1 (kg/h) | B1 cut (kg/h) at the bottom of C1 tower | C2 tower top O2 cut (kg/h) | |
| H 2O | 0.035 | 0.049 | 0.045 | 0.004 | |
| IB | 20.100 | 3.027 | 3.027 | ||
| All the other C4 | 68.365 | 68.358 | 68.358 | 0.007 | 0.007 |
| MeOH | 11.500 | 1.808 | 1.808 | ||
| MTBE | 26.337 | 0.009 | 26.329 | 25.558 | |
| MSBE | 0.010 | 0.010 | 0.008 | ||
| DME | 0.083 | 0.083 | |||
| TBA | 0.076 | 0.045 | 0.045 | ||
| DIB | 0.252 | 0.252 | 0.003 | ||
| Add up to | 100.000 | 100.000 | 73.360 | 26.640 | 25.611 |
H in table
2o represents that water, IB represent that iso-butylene, MeOH represent that methyl alcohol, MTBE represent that first class tertbutyl ether, MSBE represent methylidene sec-butyl ether, TBA represent that the trimethyl carbinol, DIB represent that Diisobutylene, DME represent dme, below identical.
Table 3
| C2 tower bottom distillate B2 (kg/h) | R2 exports cut P2 (kg/h) | C3 tower bottom distillate B3 (kg/h) | C3 overhead fraction O3 (kg/h) | T1 import wash water W1 (kg/h) | |
| H 2O | 0.003 | 0.056 | 0.076 | 6.000 | |
| IB | 14.513 | 14.513 | |||
| All the other C4 | 0.007 | 0.007 | |||
| MeOH | 8.194 | 7.721 | 0.648 | ||
| MTBE | 0.771 | 2.555 | 2.595 | ||
| MSBE | 0.002 | 0.008 | 0.016 | ||
| DME | 0.120 | 0.120 | |||
| TBA | 0.009 | 0.022 | |||
| DIB | 0.253 | 0.149 | 0.071 | ||
| Add up to | 1.029 | 25.611 | 10.501 | 15.290 | 6.000 |
Table 4
| Aqueous phase B 4 (kg/h) at the bottom of T1 tower | T1 tower top organic phase O4 (kg/h) | C5 overhead fraction O6 (kg/h) | C5 tower bottom distillate B6 (kg/h) | |
| H 2O | 5.992 | 0.008 | 0.008 | |
| IB | 14.513 | 0.239 | 14.282 | |
| All the other C4 | 0.007 | 0.007 | ||
| MeOH | 0.648 | |||
| MTBE | ||||
| MSBE | ||||
| DME | 0.072 | 0.048 | 0.048 | |
| TBA | ||||
| DIB | ||||
| Add up to | 6.713 | 14.576 | 0.295 | 14.289 |
By embodiment 2, can find out, adopt the inventive method, can obtain the polymerization-grade isoolefine product that purity is greater than 99.5%.
Claims (9)
1. an Isoolefine production method, includes following operation:
(1) hydrocarbon mixture and at least one alcohol of at least containing a kind of isoolefine are sent into the methyltertiarvbutyl ether reactor R1 that catalyst for etherification is housed, to make the product P 1 that at least contains a kind of tert-alkyl ether;
(2) product P 1 operation (1) being obtained is sent into the first separation column C1, to obtain the organic fraction O1 that mainly contains unreacted hydrocarbon mixture, unreacting alcohol, a small amount of lower molecular weight ether light constituent and the fraction B 1 that mainly contains tert-alkyl ether, secondary alkyl oxide and low polyisoolefines heavy constituent;
(3) fraction B 1 that mainly contains tert-alkyl ether, secondary alkyl oxide and low polyisoolefines heavy constituent operation (2) being obtained is sent into after-fractionating tower C2, the fraction B 2 that obtains high purity tert-alkyl ether cut O2 and contain tert-alkyl ether, secondary alkyl oxide and low polyisoolefines heavy constituent;
(4) high purity tert-alkyl ether cut O2 heater via E1 heating operation (3) being obtained, after the first compressor K1 compression, with gas phase form, send into ether cracking reactor R2 again, obtain mainly containing the product P 2 of unreacted tert-alkyl ether and isoolefine and alcohol; After further separation, obtain isoolefine again,
The working pressure of described after-fractionating tower is 0.02～2.0MPa, and stage number is 3～80;
Described ether-splitting solution reactor reaction pressure is 0.3～1.5MPa, and temperature of reaction is 50 ℃～300 ℃, and air speed is 0.5～50h
-1;
(5) product P 2 operation (4) being obtained is with the extraction of gas phase form, after being condensed as the thermal source of follow-up the 5th separation column C5 reboiler, send into the 3rd separation column C3 after the second compressor compresses, main containing the light constituent cut O3 of isoolefine, a small amount of alcohol, a small amount of lower molecular weight ether with mainly containing the fraction B 3 of alcohol, unreacted tert-alkyl ether to obtain;
The pressure of described the 3rd separation column is 0.2～1.2MPa, and stage number is 3～80.
2. Isoolefine production method as claimed in claim 1, is characterized in that:
The working pressure of described after-fractionating tower is 0.05～1.5MPa, and stage number is 10～50.
3. Isoolefine production method as claimed in claim 1, is characterized in that:
Described the 3rd separation column pressure is 0.3～0.8MPa, and stage number is 10～50.
4. Isoolefine production method as claimed in claim 1, is characterized in that comprising following operation:
The cut that the 3rd fractionation tower top obtains is sent into water wash column, to obtain the comprising water of water, alcohol and to comprise the organic phase of isoolefine, a small amount of lower molecular weight ether light constituent;
The cut that the 3rd fractionation tower top obtains is 0.005～20 with the water weight ratio that enters water wash column, and the pressure of washing disengaging zone is 0.1～2.0MPa, and temperature is 10 ℃～60 ℃.
5. Isoolefine production method as claimed in claim 4, is characterized in that:
The cut that the 3rd fractionation tower top obtains is 0.01～5 with the water weight ratio that enters described water wash column, and the pressure range of washing disengaging zone is 0.1～1.5MPa.
6. Isoolefine production method as claimed in claim 4, is characterized in that comprising following operation:
Described water is sent into the 4th separation column, with aqueous distillate and the rich alcohol cut that obtains comprising poor alcohol, the described rich alcohol cut of a part is circulated to methyltertiarvbutyl ether reactor, and the described aqueous distillate of a part is circulated to water wash column,
The pressure range of described the 4th separation column is 0.1～1.2MPa, and stage number is 3～80.
7. Isoolefine production method as claimed in claim 6, is characterized in that:
The pressure range of described the 4th separation column is that 0.1～0.8MPa stage number is 10～50.
8. Isoolefine production method as claimed in claim 6, is characterized in that comprising following operation:
The organic phase of described water wash column extraction is sent into the 5th separation column, to obtain comprising light constituent cut and the high purity isoolefine cut of lower molecular weight ether, the described light constituent cut of a part is circulated to methyltertiarvbutyl ether reactor,
Described the 5th separation column pressure is that 0.1～1.5MPa stage number is 3～80.
9. Isoolefine production method as claimed in claim 8, is characterized in that:
The pressure of described the 5th separation column is 0.3～1.0MPa, and stage number is 5～50.
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| CN102897830B (en) * | 2011-07-29 | 2014-07-09 | 中国石油化工股份有限公司 | Recovery method of polyolefin catalyst mother liquid |
| CN103172487B (en) * | 2011-12-23 | 2015-05-13 | 中国石油化工股份有限公司 | Production process of high-purity isoolefine (tert-olefin) |
| CN103172483B (en) * | 2011-12-23 | 2015-05-13 | 中国石油化工股份有限公司 | Production process of high-purity isoolefine (tert-olefin) |
| CN103804116B (en) * | 2012-11-08 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of method of methyl tertiary butyl ether cracking isobutene polymer grade |
| CN110526796B (en) * | 2019-08-30 | 2024-02-06 | 凯瑞环保科技股份有限公司 | Device and method capable of providing four-carbon raw materials for MTBE downstream device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1552679A (en) * | 2003-06-06 | 2004-12-08 | 中国石油化工股份有限公司北京燕山分 | Isoalkene producing process |
| CN1690028A (en) * | 2004-04-22 | 2005-11-02 | 中国石油化工股份有限公司 | Catalytic distillation process for olefin production device |
| US20070129588A1 (en) * | 2005-12-05 | 2007-06-07 | Kalnes Tom N | Integrated oxygenate conversion and product cracking |
-
2009
- 2009-10-30 CN CN200910236763.5A patent/CN102050690B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1552679A (en) * | 2003-06-06 | 2004-12-08 | 中国石油化工股份有限公司北京燕山分 | Isoalkene producing process |
| CN1690028A (en) * | 2004-04-22 | 2005-11-02 | 中国石油化工股份有限公司 | Catalytic distillation process for olefin production device |
| US20070129588A1 (en) * | 2005-12-05 | 2007-06-07 | Kalnes Tom N | Integrated oxygenate conversion and product cracking |
Non-Patent Citations (4)
| Title |
|---|
| 一种压缩机节能降耗技术;熊光德;《天然气与石油》;20020330;第20卷(第1期);第60-62页 * |
| 压缩机增产节能改造的措施及应用;张瑞林;《节能技术》;20000725;第18卷(第4期);第23-24、43页 * |
| 张瑞林.压缩机增产节能改造的措施及应用.《节能技术》.2000,第18卷(第4期), |
| 熊光德.一种压缩机节能降耗技术.《天然气与石油》.2002,第20卷(第1期), |
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